US20060106155A1 - Phosphite reactions in the presence of metal soaps for liquid stabilisers - Google Patents

Phosphite reactions in the presence of metal soaps for liquid stabilisers Download PDF

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US20060106155A1
US20060106155A1 US10/546,249 US54624905A US2006106155A1 US 20060106155 A1 US20060106155 A1 US 20060106155A1 US 54624905 A US54624905 A US 54624905A US 2006106155 A1 US2006106155 A1 US 2006106155A1
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organophosphite
group
phosphite
stabiliser
ester
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Charles-Antoine Carraz
Susan Malcomson
Malcolm Mellor
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Akzo Nobel NV
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Akzo Nobel NV
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Assigned to AKZO NOBEL N.V. reassignment AKZO NOBEL N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CARRAZ, CHARLES-ANTOINE, MALCOMSON, SUSAN PATRICIA, MELLOR, MALCOLM THOMAS JOHN
Publication of US20060106155A1 publication Critical patent/US20060106155A1/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/08Esters of oxyacids of phosphorus
    • C07F9/141Esters of phosphorous acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/08Esters of oxyacids of phosphorus
    • C07F9/141Esters of phosphorous acids
    • C07F9/145Esters of phosphorous acids with hydroxyaryl compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/025Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/06Homopolymers or copolymers containing elements other than carbon and hydrogen
    • C08L57/08Homopolymers or copolymers containing elements other than carbon and hydrogen containing halogen atoms

Definitions

  • the present invention relates to a novel process for the preparation of a liquid stabiliser for vinyl halide polymers comprising one or more organophosphite esters, to the thus obtained liquid stabiliser, to a stabilised vinyl halide polymer comprising said liquid stabiliser, and to shaped articles formed therefrom.
  • polymers and copolymers of vinyl chloride are utilised for the manufacture of various shaped articles by moulding, extrusion, and casting processes.
  • high temperatures up to 180-200° C. are required in order to bring the polymer to a sufficiently soft state.
  • polymers based on vinyl chloride undergo considerable degradation, which results in discolouration and a decrease of their mechanical properties.
  • stabilisers can be added to the polymer feed. It is generally known that the addition of basic substances, such as lead stearate, calcium stearate or calcium hydroxide, stabilises this type of polymer by inhibiting thermal decomposition. It was found that particularly effective stabilising compounds comprise basic metal soaps of fatty acids.
  • U.S. Pat. No. 4,102,839 discloses a stabiliser composition imparting heat resistance to vinyl chloride polymers as well as stabilisation against thermal degradation which comprises a divalent metal salt of an organic carboxylic acid and a ⁇ -diketone or ⁇ -keto-aldehyde.
  • a possible disadvantage of the use of the above-mentioned metal soap stabilisers is that due to the presence of excess carboxylate, the stabilisers can produce a greater or lesser degree of incompatibility with the vinyl halide polymer during its processing and in the finished vinyl plastic product. This results in migration of unassimilated carboxylate to the surfaces of the vinyl resin compound during curing and processing, which becomes visible by haziness or discolouration of the vinyl plastic. Moreover, undesirable plate-out on the carrying equipment is caused, as well as undesirable scum that exudes on aging or exposure to weathering. It is for instance known from U.S. Pat. No. 2,564,646 or U.S. Pat. No.
  • metal carboxylate-organophosphite ester stabiliser compositions are prepared in two steps.
  • the metal carboxylate salt is prepared, and subsequently the one or more organophosphite ester components are added.
  • the carboxylic acid components of the metal carboxylates are often mixtures of (C 6 -C 26 ) aliphatic and (C 7 -C 19 ) aromatic acids.
  • the preparation of their salts normally requires the use of a solvent to reduce the viscosity of the salts for ease of handling and to assist with the removal of water from the reaction mixture.
  • the organophosphite ester component of liquid stabilisers is generally prepared by transesterification of a triorganic phosphite or an organic acid phosphite with the desired alcohol, as is known in the art.
  • it is formed by transesterification of triphenylphosphite or diphenyl acid phosphite under elimination of phenol in the presence of a base catalyst, according to the following equations:
  • liquid stabilisers comprising triorganic phosphites and metal carboxylates.
  • the liquid stabiliser described in this document comprises barium and zinc, one or more aliphatic carboxylates selected from the group consisting of straight and branched aliphatic saturated and unsaturated carboxylates, one or more aromatic carboxylates containing 8 to 10 carbon atoms, one or more triorganic phosphites, and one or more organic acid phosphites.
  • the most preferred carboxylates are mentioned to include oleate and isomers of octanoate, such as 2-ethyl hexanoate.
  • the most convenient manner to make this stabiliser is disclosed to be admixing, in a first step, the previously prepared barium-zinc-carboxylate salt mixture, the triorganic phosphite(s) which is/are liquid at 20° C., and the organic acid phosphite(s) which is/are liquid at 20° C. Often, an amount of solvent or diluent must be added in order to prevent the mixture from becoming excessively viscous.
  • additional solid components such as additional barium and/or zinc carboxylates are added, combined with a certain amount of solvent, preferably isodecyl alcohol and mineral spirits, to provide good mixing.
  • solvent preferably isodecyl alcohol and mineral spirits
  • alcoholic solvents in the final stabiliser composition were found to have some major disadvantages. First, they tend to react with the organo-phosphite esters both during the preparation of the stabiliser and during the processing of the vinyl chloride polymer, generating phenol or alkylated phenol components. Alcoholic solvents, phenols, and alkylated phenols all contribute to the amount of undesired volatiles present during the production of the stabiliser as well as during the processing of vinyl chloride polymer and in the final shaped article.
  • liquid stabiliser composition which does not introduce volatiles to the vinyl halide products. Furthermore, it is an object of the present invention to provide a liquid stabiliser comprising one or more organophosphite esters and one or more metal carboxylates which has improved stabilising properties.
  • the objects of the invention are realised by preparing a metal carboxylate-organophosphite ester liquid stabiliser composition via an in-situ preparation process, which means that one or more organophosphite ester components are synthesised in the presence of one or more metal carboxylate components.
  • organophosphite ester used throughout this document is meant to denominate both triorganic phosphites with the general formula of P(OR) 3 , organic acid phosphites with the general formula of (RO) 2 P(O)H, and di- and polyphosphites with the general formula of RO—[P(OR)—O—R′—O] n —P(OR) 2 , wherein each R is independently selected from the group consisting of a C 7 -C 18 alkylaromatic group, a linear or branched C 6 -C 14 aliphatic group, and a phenyl group, R′ may be any conventional bridging group, and n is 1-3,000.
  • Carboxylic acids suitable for use in the process of preparing the liquid stabiliser composition according to the present invention include any conventional acid.
  • linear or branched C 6 -C 26 aliphatic acids and/or C 7 -C 19 aromatic acids are used.
  • the carboxylic acid is selected from the group consisting of benzoic acid, toluic acid, tert-butyl benzoic acid, a C 8 -C 10 aliphatic acid, and a C 18 aliphatic acid.
  • Said aliphatic acids may contain up to 3 double bonds.
  • one or more suitable carboxylic acids can be used. In a particularly preferred embodiment, a mixture of two or more carboxylic acids is employed.
  • These one or more carboxylic acids are mixed with a suitable solvent, or a mixture of suitable solvents.
  • one or more metal sources are added in a conventional amount.
  • Metal sources which are particularly suitable for this purpose include any common salts of Ca, Ba, Zn, Sr, K, and Cd, such as calcium hydroxide, calcium oxide, barium hydroxide, barium oxide, zinc oxide, strontium hydroxide, potassium hydroxide, cadmium oxide, or cadmium hydroxide.
  • two or more metal sources are used which preferably comprise salts of barium and zinc or calcium and zinc.
  • Suitable solvents for the process according to the present invention are hydroxylic solvents which are able to transesterify organophosphite esters to form different organophosphite esters. Hence, they are called “organophosphite ester-reactive solvents” throughout this specification.
  • a solvent is considered to be able to react with organophosphite esters if in a 50/50 molar mixture of said solvent and said organophosphite ester, in the presence of 1 mol % potassium hydroxide or other suitable catalyst, at least 10 mol % of the solvent has reacted with the organophosphite ester after heating the mixture for 2 hours at 140° C.
  • triphenyl phosphite is used as the organophosphite and KOH as the catalyst if a screening for a suitable solvent is conducted. It is important that these solvents are so low-volatile that they do not come off with the generated water in the first step of the process. It is noted that the term ulow-volatilen therefore denotes solvents having a boiling point higher than water.
  • the organophosphite ester-reactive solvent is selected from the group of low-volatile alcohols and glycols.
  • a non-restrictive list of alcohols which may be used includes C 6 -C 14 straight or branched alcohol, isodecanol, tridecanol, technical mixtures of alcohols, 2-ethyl hexanol, butyldioxitol, methyldioxitol, butylphenol, dibutylphenol, tributylphenol, and 2,4-dicumylphenol.
  • a non-restrictive list of polyols which may be used includes 1,2-ethanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, polyethylene glycol, bisphenol A, and bisphenol F.
  • the organophosphite ester-reactive solvent is selected from the group consisting of 2-ethylhexanol, isodecanol, and tridecanol. Most preferably, isodecanol or tridecanol is used. In the process according to the invention, a mixture of two or more of the above-mentioned organophosphite ester-reactive solvents can be employed. However, preferably one single solvent is used.
  • the organophosphite ester comprises at least one C 7 -C 18 alkylaromatic group, but most preferably, the organophosphite ester comprises at least one phenyl group.
  • a non-limiting list of exemplary additional organophosphite esters that can be used in this invention includes tetraphenyl dipropylene-glycol diphosphite, diphenyl pentaerythritol diphosphite, poly-4,4′-isopropylidenediphenol tetraphenol phosphite, and poly(dipropylene glycol) phenyl phosphite.
  • the organophosphite ester is preferably selected from the group consisting of diphenylisodecyl phosphite, phenyldiisodecyl phosphite, trinonylphenyl phosphite, butyldioxityl nonylphenyl phenylphosphite, butyldioxityl dinonylphenyl phosphite, dibutyldioxityl nonylphenyl phosphite, tetraphenyl dipropylene-glycol diphosphite, and diphenyl acid phosphite.
  • the organophosphite ester added to the one or more metal carboxylate salts is triphenyl phosphite, because it is readily available and inexpensive.
  • organophosphite esters Upon reaction of the one or more organophosphite esters with the one or more organophosphite ester-reactive solvents (i.e. a transesterification reaction), compounds with the general formula of ROH are liberated, wherein R, depending on the organophosphite ester used, is a C 7 -C 18 alkylaromatic group, a linear or branched C 6 -C 14 aliphatic group, or a phenyl group. Since, preferably, at least one of the R groups in the organophosphite ester is a C 7 -C 18 alkylaromatic group, preferably, at least one equivalent of a phenol-derived product is generated.
  • At least one of the R groups in the organophosphite ester is a phenyl group, which means that in a particularly preferred embodiment, at least one equivalent of phenol is liberated.
  • the removal of the generated aliphatic or aromatic alcohols takes place at a temperature of preferably at least 160° C., more preferably at least 170° C., and most preferably at least 180° C., and at a vacuum of preferably less than 40 mmHg, more preferably less than 25 mmHg, and most preferably less than 20 mmHg.
  • the temperature at which essentially all generated aliphatic alcohols, phenol and phenol-derived products are distilled off does not exceed 240° C., more preferably 230° C., and most preferably 210° C.
  • the vacuum preferably is not less than 4 mmHg, more preferably not less than 6 mmHg, and most preferably not less than 8 mmHg.
  • excess organophosphite ester-reactive solvent in the stabiliser composition which has not reacted with the organophosphite esters is also removed in this step.
  • At least 70 wt %, more preferably, at least 85 wt %, even more preferably, at least 95 wt %, and most preferably, essentially all organophosphite esters present in the final composition are products of the reaction between the organophosphite ester used as the starting material and the one or more organophosphite ester-reactive solvents.
  • the resulting organophosphite ester components will show very little subsequent transesterification during stabiliser manufacture or storage, as essentially no organophosphite ester-reactive solvent remains, and hence, very little phenol or alkylated phenol will be liberated.
  • Organophosphite esters which are preferably formed in the in-situ process according to the present invention comprise diphenylisodecyl phosphite, phenylisodecyl phosphite, triisodecyl phosphite, and tris(tridecyl)phosphite.
  • antioxidants may be added to the liquid stabiliser composition.
  • the addition can take place before, during, or after the addition of the one or more organophosphite esters to the reaction mixture.
  • the stabiliser composition according to the present invention does not comprise sulphur-containing organo tin compounds.
  • the liquid stabiliser composition according to the present invention obtainable via the process described above preferably has a viscosity of at most 20 Pa ⁇ s, more preferably at most 5 Pa ⁇ s, most preferably at most 2.5 Pa ⁇ s, at 20° C. in order to facilitate handling.
  • the viscosity of the final stabiliser is at least 10 mPa ⁇ s, most preferably at least 20 mPa ⁇ s.
  • the one or more metal carboxylates are preferably present in an amount of at least 5 wt % based on the total weight of the final liquid stabiliser. More preferably, they are present in an amount of at least 10 wt %, most preferably at least 15 wt %.
  • the maximum amount of the one or more metal carboxylates in the final stabiliser composition preferably is 90 wt %, based on the total weight of the final liquid stabiliser. More preferably, at most 85 wt %, most preferably at most 80 wt % of metal carboxylates is present in the stabiliser composition.
  • the total amount of organophosphite ester-reactive solvent employed in the process preferably is at least 5 wt %, based on the total weight of organophosphite esters used as the starting material, more preferably at least 10 wt %, and most preferably at least 20 wt %.
  • the maximum amount of organophosphite ester-reactive solvent preferably is 99 wt %, based on the total weight of the organophosphite esters used as the starting material. More preferably, the amount of organophosphite ester-reactive solvent is at most 97 wt %, and most preferably at most 95 wt %, based on the total weight of organophosphate esters used as the starting material.
  • 25-100 wt % of the organophosphite ester-reactive solvent(s) will react with the organophosphite ester(s) that is/are added to said organophosphite ester-reactive solvent(s). More preferably, 50-99 wt %, most preferably 75-98 wt % of the organophosphite ester-reactive solvent(s) will react with the organophosphite ester(s) that is/are added to the organophosphite ester-reactive solvent(s).
  • organophosphite ester-reactive solvent in the final liquid stabiliser nearly all organophosphite ester-reactive solvent will be bound in organophosphite esters, with almost no free solvent remaining.
  • essentially all organophosphite ester-reactive solvent will be bound in organophosphite esters, which means that the final liquid stabiliser is essentially solvent-free.
  • essentially solvent-free is meant that the maximum total amount of unreacted organophosphite ester-reactive solvent, preferably alcohol or glycol, which is present in the final stabiliser composition does not exceed 5.0 wt %, based on the total weight of the final liquid stabiliser. More preferably, the maximum total amount of unreacted organophosphite ester-reactive solvent is 2.5 wt % and most preferably 1.0 wt %, based on the total weight of the final liquid stabiliser.
  • the amount of phenol or phenol-derived products present in the final stabiliser composition is less than 5.0 wt %, more preferably less than 3.0 wt %, and most preferably less than 2.0 wt %, based on the total weight of the final liquid stabiliser.
  • the one or more organophosphite esters which are present in the final liquid stabiliser composition are preferably present in an amount of at least 5 wt %, based on the total weight of the final liquid stabiliser. More preferably, they are present in an amount of at least 10 wt %, most preferably at least 15 wt %, based on the total weight of the final liquid stabiliser.
  • the maximum amount of the one or more organophosphite esters in the final stabiliser composition preferably is 95 wt %, based on the total weight of the final liquid stabiliser. More preferably, at most 90 wt % of organophosphite esters is present, most preferably at most 85 wt %.
  • the liquid stabiliser composition obtainable by the process according to the invention can additionally contain conventional additives such as antioxidants, plasticisers, metal intermediates, costabilisers, triorganic phosphites and diphosphites, organic acid phosphites, lubricants, costabilisers, and the like.
  • the final liquid stabiliser is diluted with phthalate ester and/or epoxy compounds or other diluents which are acceptable in the vinyl halide polymer, for example since they are conventionally used plasticisers.
  • the liquid stabiliser according to the present invention can be blended with vinyl halide polymers in order to improve their heat-stability.
  • Vinyl halide polymers which can be used are any polymer formed at least in part of the recurring group (—CHX——(CH 2 ) n and having a halide content in excess of 40%.
  • n is the number of units in the polymer chain and X is a halide.
  • the polymer is a vinyl chloride polymer.
  • the polymer can also be a copolymer of vinyl chloride with other copolymerisable monomers in moderate proportion, such as copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride with maleic or fumaric acids or esters, and copolymers of vinyl chloride with styrene.
  • the stabiliser composition according to the present invention is also effective with mixtures of polyvinyl chloride in major proportion with a minor proportion of other synthetic resins such as chlorinated polyethylene or a copolymer of acrylonitrile, butadiene, and styrene.
  • the amounts of the liquid stabiliser according to the present invention which are incorporated into the vinyl halide polymers for enhancing the resistance to heat-mediated deterioration and improved clarity are small.
  • the liquid stabiliser according to the invention is added to the polymer in an amount of at least 0.1 wt %, based on the total weight of the stabilised polymer. More preferably, the stabiliser is present in an amount of at least 0.5 wt %, and most preferably in an amount of at least 1.0 wt %, based on the total weight of the stabilised polymer.
  • the maximum amount of liquid stabiliser to be added to the vinyl halide polymer preferably is no more than 15 wt %, based on the total weight of the stabilised polymer. More preferably, the amount of liquid stabiliser is at most 10 wt %, most preferably at most 5 wt %, based on the total weight of the stabilised polymer.
  • the preparation process provides several unexpected advantages in the performance of the stabiliser. These include increasing the heat stability in some applications and a notable increase in the clarity of the finished polymer article. A further additional benefit can be observed when the stabiliser is used in combination with isocyanate based bonding agents needed to improve the adhesion of PVC plastisols to a fabric substrate, i.e. in the production of coated fabrics such as tarpaulins, conveyor belts, waterproof clothing. In this application the stabiliser and the bonding agent are incorporated into the pasted PVC plastisol prior to the coating process.
  • the isocyanate is extremely reactive and it is a known problem for the PVC processor that the viscosity of the paste will increase on storage and in a relatively short space of time a point will be reached where the paste can no longer be conveniently spread onto the fabric. This is known within the industry as the “pot life” of the plastisol paste. Stabilisers prepared by the process according to the present invention contain reduced amounts of chemical compounds which can react with isocyanates. The result is a marked increase in the “pot life” of the plastisol and improved convenience for the processor.
  • a reaction vessel was charged with isodecanol (229.3 g), p-tert-butylbenzoic acid (100 g), and versatic C10 acid (190.7 g). The resulting mixture was heated to 80° C. Zinc oxide (30.0 g) and barium hydroxide octahydrate (145.6 g) were added portionwise and the reaction mixture was then stirred for 30 min. Subsequently, the resulting soap was dehydrated at 110° C. at 15 mmHg and brought under a nitrogen atmosphere. Triphenyl phosphite (449.9 g) was added and the resulting mixture was heated to 140° C. and stirred for 3 hours.
  • a reaction vessel was charged with isodecanol (229.3 g), p-tert-butylbenzoic acid (100 g), and versatic C10 acid (190.7 g). The resulting mixture was heated to 80° C. Zinc oxide (30.0 g) and barium hydroxide octahydrate (145.6 g) were added portionwise and the reaction mixture was then stirred for 30 min. Subsequently, the resulting soap was dehydrated at 110° C. at 15 mmHg and brought under a nitrogen atmosphere. The reaction mixture was allowed to cool down to 90° C.
  • composition A Suspension polymerised PVC resin (K-71) 100 Diisononyl phthalate 45 Epoxidised Soybean Oil 2
  • Example 2 Stearic acid 0.3

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US10/546,249 2003-04-04 2004-03-23 Phosphite reactions in the presence of metal soaps for liquid stabilisers Abandoned US20060106155A1 (en)

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EP03076007.8 2003-04-04
EP03076007 2003-04-04
PCT/EP2004/003067 WO2004087722A1 (en) 2003-04-04 2004-03-23 Phosphite reactions in the presence of metal soaps for liquid stabilisers

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EP (1) EP1611142A1 (enrdf_load_stackoverflow)
JP (1) JP2006522185A (enrdf_load_stackoverflow)
KR (1) KR20060002899A (enrdf_load_stackoverflow)
CN (1) CN1768068A (enrdf_load_stackoverflow)
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CN109054082B (zh) * 2018-07-23 2020-04-28 浙江锦润生物科技有限公司 一种含有亚磷酸有机酯稳定剂及其合成方法

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EP2886594A1 (en) * 2013-12-18 2015-06-24 Baerlocher GmbH Liquid zinc salt preparation as stabilizer for halogenated polymers

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JP2006522185A (ja) 2006-09-28
WO2004087722A1 (en) 2004-10-14

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